CN110327905A - A kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base - Google Patents

A kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base Download PDF

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CN110327905A
CN110327905A CN201910724338.4A CN201910724338A CN110327905A CN 110327905 A CN110327905 A CN 110327905A CN 201910724338 A CN201910724338 A CN 201910724338A CN 110327905 A CN110327905 A CN 110327905A
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compound
carbon nanotube
walled carbon
hydrochloric acid
polyaniline
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周志斌
毛松柏
陈小花
朱道平
陈园园
杨绪甲
余勇
宋丽
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China Petroleum and Chemical Corp
China Petrochemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petrochemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Abstract

The invention discloses a kind of preparation method of the nitrogenous porous carbon nano-composite material of Polymerization of Polyaniline/carbon Nanotube base, it can be achieved that CO2 gas absorption separates.The present invention is using multi-walled carbon nanotube as substrate, it is aoxidized using nitration mixture, generate the band carboxyl multi-walled carbon nanotube for being soluble in solution, in situ chemical oxidative polymerization reaction occurs by aniline monomer, so that polyaniline-coated is in multi-wall carbon nano-tube pipe surface, polyaniline/multi-walled carbon nanotube the nanocomposite coaxially coated is generated, the nitrogenous porous carbon nano-composite material coaxially coated is generated finally by a step activation method high-temperature roasting.Compared with conventional solid-state adsorbent, the composite material has good high-specific surface area, high porosity, thermal stability, adsorbable CO2 gas and regeneration energy consumption is low, adsorption desorption cycle performance is splendid, raw material is easy to get, the advantages such as at low cost, it is a kind of New Solid adsorbent efficiently, environmentally friendly, therefore has more good application prospect and environmental improvement benefit.

Description

A kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base
Technical field
The invention belongs to nano material and gas technical field of adsorptive separation engineering, the present invention discloses a kind of polyaniline/carbon The nitrogenous porous carbon nano-composite material preparation method of nanotube base.
Background technique
Energy and environment are world today's two principal themes.A large amount of uses of fossil energy (predominantly coal, natural gas), promote One booming industrial age, such as power plant, petrochemical industry, steel industry etc..Meanwhile the temperature based on CO2 A large amount of discharges of room gas, can generate " greenhouse effects " and lead to global warming, and then on initiation Melting Glacierss, sea level The extreme events such as liter, desertification influence the living environment and life of the mankind.Therefore, alleviate greenhouse gases to bring to the mankind Immense pressure, key be to fossil energy generate CO2 trapped and sealed up for safekeeping, this is also the hot spot of industrial research.
The method of industrial trapping CO2 is broadly divided at present: solvent absorption, membrane separation process, solid absorption method and several Kind method is used in combination.Solvent absorption includes Physical Absorption method and chemical absorption method, and wherein Physical Absorption method is suitable for CO2 Higher situation is divided, but lower to the removal efficiency of CO2;Chemical absorption method mainly makees lyosoption with chain hydramine, and technology is It is quite mature, but easily cause equipment corrosion and regeneration energy consumption height.Membrane separation process is at low cost, is readily synthesized, separating property height, but It is limited by self property, easy to aging, pollution, not easy cleaning.Solid absorption method refer to using solid absorbent to CO2 into The novel C O2 adsorption separating method of the method for row adsorbing separation and a kind of great application prospect, be broadly divided into physical absorption and Chemisorption, the physical absorbent by taking active carbon, molecular sieve etc. as an example, heat of adsorption is lower, is applied to cryogenic absorption more, with The raising of temperature, absorption property reduce obvious and not high to the selectivity of CO2 absorption;Hydrotalcite-based compound and other oxides The chemosorbent that can be chemically reacted with CO2, though there is high selectivity to CO2, in desorption, there are regenerabilities The disadvantages of difference, high energy consumption.Therefore, a kind of that there is high specific surface area, large hole appearance and the good carbon-based solid of absorption property to inhale Attached dose more has competitiveness.
Carbon-based adsorbent as solid absorbent a kind of novel and with applications well prospect, it is at low cost, be easily-synthesized, Physicochemical properties are stable, regeneration energy consumption is low, the rate of adsorption is fast, the favor by lot of domestic and international scholar and researcher.Mesh Preceding existing carbon-based material report much relevant to CO2 absorption, including activated carbon fibre, ordered porous carbon material, graphene etc., And adsorption effect is good, such as T. Liang (Langmuir 2016,32,8,042 8049), M. E. Casco etc. (Carbon, 67 (2014) 230-235) and patent CN101890340A etc..Carbon-based adsorbent is largely that solid amine is inhaled Attached dose and polymer with nitrogen adsorbent etc..Solid amine absorption agent generally passes through Graft Method, infusion process gathers organic amine or amino It closes in object modification to porous carbon sill of sheet, occurs to chemically react by amine and CO2 to improve CO2 adsorbance;Polymer with nitrogen one As can by be carbonized, activate and etc. further obtain biggish specific surface area, hole hold and increase the adsorbance of CO2.However, solid State amine absorber thermal stability is poor, amine is volatile, the disadvantages of operating condition is mild and regeneration requirements are high is needed to make it in work under high temperature It applies and is restricted in industry;Though there is polymer with nitrogen high-specific surface area, large hole to hold, its mechanical performance is poor, thermostabilization Property difference etc., also can not industrially be widely applied.
Multi-walled carbon nanotube structural integrity, it is both big with the intrinsic person's character of carbon materials, such as light weight, draw ratio, Electrical and thermal conductivity with metal material, also with the heat-resisting and corrosion resistance etc. of ceramic material.Multi-walled carbon nanotube is as multiple Condensation material reinforcement shows good intensity, elasticity, fatigue resistance etc., is a kind of in the great application potential of every field Carbon fibre material, high-specific surface area, thermal stability are good, electric conductivity is good makes it have bright application in CO2 adsorbing domain Prospect.Multi-walled carbon nanotube surfacing, defect is few, so that it had both been insoluble in organic solvent or is insoluble in water, so showing Inertia, it is difficult to be reacted with the participation of other substances, therefore it is limited in the application in many fields.But by the concentrated sulfuric acid, concentrated nitric acid with Certain volume carries out oxidation processes to it than nitration mixture obtained, its surface defect is oxidized to carboxyl, and then change its dissolubility And dispersibility.Polyaniline is a kind of nitrogenous conductive polymer material, because its raw material is easy to get, synthesis technology is simple, unique doping The features such as phenomenon, chemistry and environmental stability are good is widely studied and applies.If multi-walled carbon nanotube and polyaniline are answered It closes, plays the synergistic effect of the two to improve the performance of material, allow composite material that both there is high-specific surface area, good thermostabilization Property, and there is nitrogen-containing group, electric conductivity and performance can be adulterated, it is applied to CO2 adsorbing domain.
Currently, this field major part researcher, which generallys use solid amine, carries out adsorbing separation to CO2, or utilize two steps Carbonizatin method come handle polymer with nitrogen with prepare solid adsorbent carry out CO2 adsorbing separation.But existing solid amine absorption agent exists The big and traditional two step carbonization preparation process of volatile under higher temperature, adsorption desorption poor circulation, regeneration energy consumption it is cumbersome, , the deficiencies such as controllable degree low unfriendly to environment, not only specific surface area is small for the solid absorbent of preparation, Kong Rong little, porosity are low, The rate of adsorption is slow, and thermal stability is low, adsorption desorption cycle performance is weak, regeneration energy consumption is high.
Summary of the invention
1, technical problem to be solved:
Existing solid amine absorption agent is volatile at relatively high temperatures, adsorption desorption poor circulation, regeneration energy consumption are big and traditional Cumbersome, the deficiencies such as unfriendly to environment, controllable degree is low of two step carbonization preparation process.
2, technical solution:
In order to solve problem above, the present invention provides a kind of nitrogenous porous carbon nano-composite material systems of polyaniline carbon nanotube base Preparation Method, comprising the following steps: step 1: the processing of multi-walled carbon nanotube substrate carboxylation, specifically: by multi-walled carbon nanotube and mix Acid flows back at 80-100 DEG C and stirs 80-100 min, then cools to room temperature, filters after being diluted with distilled water, with anhydrous second Alternately washing composite material is until neutral for pure and mild deionized water, and then 55-65 DEG C of drying in a vacuum drying oven, pulverizes End;Step 2: the quality of multi-walled carbon nanotube and aniline monomer is respectively 3-30:1, is dissolved in 1 that volume is 150 mL Become mixed solution in the aqueous hydrochloric acid solution of mol/L, under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, by institute It states mixed solution to go in three-necked flask, is persistently stirred to react 5-7 h, 25-35 min is then stirred by ultrasonic, step 3: weighing In the aqueous hydrochloric acid solution for the 1mol/L that ammonium sulfate 3-3.5 g is dissolved in 50 mL, U-shaped constant pressure titration funnel is poured into after ultrasonic vibration, 30 It is added drop-wise in three-necked flask in min;Step 4: 5-7 h is reacted at 0-5 DEG C, product ethyl alcohol, the deionization that reaction is obtained Water alternately washs, centrifugation, until product is in neutrality, then freeze-drying process, and grind into powder.
Further include step 5, weighs compound made from the potassium hydroxide and step 4 that mass ratio is 1:4 and use glass in porcelain boat The stirring of glass stick in tube furnace until uniformly, once activated, compound is in 200 DEG C of 1 h of activation, then at 300-700 DEG C 1-3h is activated, step 6: by the compound after activation first with acid processing, then alternately being washed with ethyl alcohol, deionized water, centrifugation, directly It is in neutrality to product, is finally placed in 50-70 DEG C of drying in vacuum oven, grind into powder.
In step 4, the freeze-drying process is that product liquid-nitrogen freeze drying is subsequently placed in freeze drier It is handled under being 18-22 Pa in -45 DEG C to -55 DEG C, vacuum degree.
Logical nitrogen rate is 55-65 mL/min.
In step 4, centrifugal rotational speed is 6000-8000 r/min.
In step 6, centrifugal rotational speed is 6000-8000 r/min.
In step 6, the sour hydrochloric acid for mass ratio 10% in the acid processing.
The nitration mixture is that 3:1 is mixed by volume for the concentrated sulfuric acid, concentrated nitric acid.
The aqueous hydrochloric acid solution is that the concentrated hydrochloric acid for being 36-38% by concentration is diluted to 0.9-1.1 in deionized water The hydrochloric acid solution of mol/L.
The multi-walled carbon nanotube, caliber are 10-30 nm, and length is 1-3 μm.
3, the utility model has the advantages that
Compared with prior art, advantage of the invention is that raw material is easy to get, is at low cost, preparation process route is simple, can carry out again Raw recycling, environmentally protective, CO2 gas absorption effect is good.Two-step method, preparation method are re-activated compared to traditional first carbonization Simpler, specific surface area and porosity are higher;Compared to conventional solid-state amine absorber, thermal stability is good, avoids higher temperature Volatile drawback, and adsorption desorption cycle performance is splendid, regeneration energy consumption is low, and it is reusable, avoid the wasting of resources, more ring It protects and industrial amplification advantage.
Detailed description of the invention
Fig. 1 is polyaniline/multi-walled carbon nanotube nanocomposite.
Fig. 2 is the nitrogenous porous carbon nano-composite material picture of Polymerization of Polyaniline/carbon Nanotube base.
Polyaniline/carbon nanometer after (a)-(c) is polyaniline/multi-wall carbon nano-tube composite material (1:1) and activates in Fig. 3 Nitrogenous porous carbon nano-composite material (1:1,600oC, 2:1) the SEM figure of pipe base.
Fig. 4 is the nitrogenous porous carbon nano-composite material of Polymerization of Polyaniline/carbon Nanotube base and other associated materials XRD spectras.
Fig. 5 is the nitrogenous porous carbon nano-composite material of Polymerization of Polyaniline/carbon Nanotube base and other associated materials graph of pore diameter distribution And other graph of pore diameter distribution and dependency structure physical parameter table.
Fig. 6 is CO2 adsorption isotherm under the nitrogenous porous carbon nano-composite material different temperatures of Polymerization of Polyaniline/carbon Nanotube base.
Fig. 7 is the nitrogenous porous carbon nano-composite material adsorption-desorption regeneration cycle of Polymerization of Polyaniline/carbon Nanotube base.
Specific embodiment
Below by embodiment, the present invention is described in detail.
For embodiment 1. using the multi-walled carbon nanotube after carboxylation as substrate, aniline monomer is carbon source and nitrogen source, and ammonium persulfate is Oxidant, aqueous hydrochloric acid solution are solvent, under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, at tri- mouthfuls of 500 mL In flask, it is persistently stirred to react 6 h.Wherein the quality of multi-walled carbon nanotube and aniline monomer is respectively 2.0 g and 0.6 g, will 30 min are stirred by ultrasonic in its aqueous hydrochloric acid solution for being dissolved in 1 mol/L that volume is 150 mL, until being uniformly mixed, ammonium persulfate 3.34 g are dissolved in the aqueous hydrochloric acid solution of the 1mol/L of 50 mL, pour into U-shaped constant pressure titration funnel after ultrasonic vibration, in 30 min It is added drop-wise in three-necked flask.After the reaction was completed, product ethyl alcohol and deionized water are alternately washed, it is compound until neutral Object abbreviation: M-P(x:y), x represents aniline quality, and y represents 10 times of multi-walled carbon nanotube quality.Then compound is carried out cold Dry, 100 DEG C of vacuum drying 10 h of degassing are lyophilized, finally to compound progress CO2 saturation absorption.The compound specific surface area of synthesis For 56.05 m2/g, 0.26 cm3/g of Kong Rongwei, average pore size is 23.89 nm, and the material is full to CO2 in 25 DEG C, 500 kPa It is 0.72 mmol/g with adsorbance.
For embodiment 2. using the multi-walled carbon nanotube after carboxylation as substrate, aniline monomer is carbon source and nitrogen source, and ammonium persulfate is Oxidant, aqueous hydrochloric acid solution are solvent, under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, at tri- mouthfuls of 500 mL In flask, it is persistently stirred to react 6 h.Wherein the quality of multi-walled carbon nanotube and aniline monomer is respectively 2.0 g and 0.4 g, will 30min is stirred by ultrasonic in its aqueous hydrochloric acid solution for being dissolved in 1 mol/L that volume is 150 mL, until being uniformly mixed, ammonium persulfate 3.34 g are dissolved in the aqueous hydrochloric acid solution of the 1mol/L of 50 mL, pour into U-shaped constant pressure titration funnel after ultrasonic vibration, in 30 min It is added drop-wise in three-necked flask.After the reaction was completed, product ethyl alcohol and deionized water are alternately washed, it is compound until neutral Object abbreviation: M-P(x:y), x represents aniline quality, and y represents 10 times of multi-walled carbon nanotube quality.Then compound is freezed Dry, 100 DEG C of vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to compound.The compound specific surface area of synthesis is 0.21 cm3/g of 55.72 m2/g, Kong Rongwei, average pore size are 20.08 nm, which is saturated CO2 in 25 DEG C, 500 kPa Adsorbance is 0.69 mmol/g.
For embodiment 3. using the multi-walled carbon nanotube after carboxylation as substrate, aniline monomer is carbon source and nitrogen source, and ammonium persulfate is Oxidant, aqueous hydrochloric acid solution are solvent, under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, at tri- mouthfuls of 500 mL In flask, it is persistently stirred to react 6 h.Wherein the quality of multi-walled carbon nanotube and aniline monomer is respectively 2.0 g and 0.2 g, will 30 min are stirred by ultrasonic in its aqueous hydrochloric acid solution for being dissolved in 1 mol/L that volume is 150 mL, until being uniformly mixed, ammonium persulfate 3.34 g are dissolved in the aqueous hydrochloric acid solution of 1 mol/L of 50 mL, pour into U-shaped constant pressure titration funnel after ultrasonic vibration, in 30 min It is added drop-wise in three-necked flask.After the reaction was completed, product ethyl alcohol and deionized water are alternately washed, it is compound until neutral Object abbreviation: M-P(x:y), x represents aniline quality, and y represents 10 times of multi-walled carbon nanotube quality.Then compound is carried out cold Dry, 100 DEG C of vacuum drying 10 h of degassing are lyophilized, finally to compound progress CO2 saturation absorption.The compound specific surface area of synthesis For 86.87 m2/g, 0.22 cm3/g of Kong Rongwei, average pore size is 23.03 nm, and the material is full to CO2 in 25 DEG C, 500 kPa It is 1.03 mmol/g with adsorbance.
For embodiment 4. using the multi-walled carbon nanotube after carboxylation as substrate, aniline monomer is carbon source and nitrogen source, and ammonium persulfate is Oxidant, aqueous hydrochloric acid solution are solvent, under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, at tri- mouthfuls of 500 mL In flask, it is persistently stirred to react 6 h.Wherein the quality of multi-walled carbon nanotube and aniline monomer is respectively 2.0 g and 0.1g, by it It is dissolved in the aqueous hydrochloric acid solution for 1 mol/L that volume is 150 mL and 30 min is stirred by ultrasonic, until being uniformly mixed, ammonium persulfate 3.34 g are dissolved in the aqueous hydrochloric acid solution of 1 mol/L of 50 mL, pour into U-shaped constant pressure titration funnel after ultrasonic vibration, in 30 min It is added drop-wise in three-necked flask.After the reaction was completed, product ethyl alcohol and deionized water are alternately washed, it is compound until neutral Object abbreviation: M-P(x:y), x represents aniline quality, and y represents 10 times of multi-walled carbon nanotube quality.Then answering each ratio It closes object to be freeze-dried, 100 DEG C of vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to the compound of each ratio. The compound specific surface area of synthesis is 86.75 m2/g, and 0.45 cm3/g of Kong Rongwei, average pore size is 24.03 nm, which exists 25 DEG C, 500 kPa to CO2 saturated extent of adsorption be 0.75 mmol/g.
For embodiment 5. using the multi-walled carbon nanotube after carboxylation as substrate, aniline monomer is carbon source and nitrogen source, and ammonium persulfate is Oxidant, aqueous hydrochloric acid solution are solvent, under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, at tri- mouthfuls of 500 mL In flask, it is persistently stirred to react 6 h.Wherein the quality of multi-walled carbon nanotube and aniline monomer is respectively 2.0 g and 0.067g, will 30 min are stirred by ultrasonic in its aqueous hydrochloric acid solution for being dissolved in 1 mol/L that volume is 150 mL, until being uniformly mixed, ammonium persulfate 3.34 g are dissolved in the aqueous hydrochloric acid solution of the 1mol/L of 50 mL, pour into U-shaped constant pressure titration funnel after ultrasonic vibration, in 30 min It is added drop-wise in three-necked flask.After the reaction was completed, product ethyl alcohol and deionized water are alternately washed, it is compound until neutral Object abbreviation: M-P(x:y), x represents aniline quality, and y represents 10 times of multi-walled carbon nanotube quality.Then answering each ratio It closes object to be freeze-dried, 100 DEG C of vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to the compound of each ratio. The compound specific surface area of synthesis is 45.01 m2/g, and 0.23 cm3/g of Kong Rongwei, average pore size is 21.45 nm, which exists 25 DEG C, 500 kPa to CO2 saturated extent of adsorption be 0.65mmol/g.
It can be seen that compound obtained in embodiment 3 from above 5 embodiments and carry out CO2 saturation absorption.Synthesis is answered Conjunction object specific surface area is 86.87 m2/g, and 0.22 cm3/g of Kong Rongwei, average pore size is 23.03 nm, and the material is in 25 DEG C, 500 KPa is 1.03 mmol/g to CO2 saturated extent of adsorption.Adsorbance is optimal, and compound is M-P(1:1 in embodiment 3).
For good adsorption effect, the present invention is to M-P(x:y) it is activated at 300-700300-700 DEG C.
Due to the M-P(1:1 in embodiment 3) adsorbance it is optimal, for more preferably effect so selecting to M-P(1:1) It is activated.
Embodiment 6
The compound of the best ratio of adsorbance --- M-P(1:1) activates it from 300-700 DEG C.Weigh certain matter The potassium hydroxide and compound (KOH: compound=2, mass ratio) of amount are stirred with glass bar up to uniform, in tubular type in porcelain boat It is once activated in furnace.Compound, then in 300 DEG C of 2 h of activation, obtains five kinds of products, by product in 200 DEG C of 1 h of activation It is alternately washed with ethyl alcohol and deionized water, until neutral, the compound abbreviation M-P(1:1, z, a:b), wherein z is represented Activation temperature, a represent the quality of potassium hydroxide, and b represents the quality of compound, then the compound be M-P(1:1,300,2: 1).100 DEG C of vacuum drying 10 h of degassing, finally carry out CO2 saturation absorption to the compound of each temperature.Compound after activation Specific surface area is 26.78 m2/g, and 0.13 cm3/g of Kong Rongwei, average pore size is 22.94 nm, and the material is in 25 DEG C, 500 kPa It is 1.70 mmol/g to CO2 saturated extent of adsorption.
Embodiment 7
The compound of the best ratio of adsorbance --- M-P(1:1) is activated in 400 DEG C.Weigh the hydrogen of certain mass Potassium oxide and compound (KOH: compound=2, mass ratio) in porcelain boat with glass bar stirring until uniformly, in tube furnace into The primary activation of row.Compound, then in 400 DEG C of 2 h of activation, obtains five kinds of products, by product ethyl alcohol in 200 DEG C of 1 h of activation It is alternately washed with deionized water, until neutral, the compound abbreviation M-P(1:1, z, a:b), wherein z represents activation temperature Degree, a represents the quality of potassium hydroxide, and b represents the quality of compound, then the compound is M-P(1:1, and 400,2:1).100℃ Vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to the compound of each temperature.Compound specific surface area after activation For 19.29 m2/g, 0.026 cm3/g of Kong Rongwei, average pore size is 10.55 nm, and the material is full to CO2 in 25 DEG C, 500 kPa It is 1.89 mmol/g with adsorbance.
Embodiment 8
The compound of the best ratio of adsorbance --- M-P(1:1) is activated in 500 DEG C.Weigh the hydrogen of certain mass Potassium oxide and compound (KOH: compound=2, mass ratio) in porcelain boat with glass bar stirring until uniformly, in tube furnace into The primary activation of row.Compound, then in 500 DEG C of 2 h of activation, obtains five kinds of products, by product ethyl alcohol in 200 DEG C of 1 h of activation It is alternately washed with deionized water, until neutral, the compound abbreviation M-P(1:1, z, a:b), wherein z represents activation temperature Degree, a represents the quality of potassium hydroxide, and b represents the quality of compound, then the compound is M-P(1:1, and 500,2:1).100℃ Vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to the compound of each temperature.Compound specific surface area after activation For 611.41 m2/g, 0.081 cm3/g of Kong Rongwei, average pore size is 4.83 nm, and the material is full to CO2 in 25 DEG C, 500 kPa It is 2.06 mmol/g with adsorbance.
Embodiment 9
The compound of the best ratio of adsorbance --- M-P(1:1) is activated in 600 DEG C.Weigh the hydrogen of certain mass Potassium oxide and compound (KOH: compound=2, mass ratio) in porcelain boat with glass bar stirring until uniformly, in tube furnace into The primary activation of row.Compound, then in 600 DEG C of 2 h of activation, obtains five kinds of products, by product ethyl alcohol in 200 DEG C of 1 h of activation It is alternately washed with deionized water, until neutral, the compound abbreviation M-P(1:1, z, a:b), wherein z represents activation temperature Degree, a represents the quality of potassium hydroxide, and b represents the quality of compound, then the compound is M-P(1:1, and 600,2:1).100℃ Vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to the compound of each temperature.Compound specific surface area after activation For 1119.14 m2/g, 0.60 cm3/g of Kong Rongwei, average pore size is 2.80 nm, and the material is full to CO2 in 25 DEG C, 500 kPa It is 2.63 mmol/g with adsorbance.
Embodiment 10
The compound of the best ratio of adsorbance --- M-P(1:1) is activated in 700 DEG C.Weigh the hydrogen of certain mass Potassium oxide and compound (KOH: compound=2, mass ratio) in porcelain boat with glass bar stirring until uniformly, in tube furnace into The primary activation of row.Compound, then in 700 DEG C of 2 h of activation, obtains five kinds of products, by product ethyl alcohol in 200 DEG C of 1 h of activation It is alternately washed with deionized water, until neutral, the compound abbreviation M-P(1:1, z, a:b), wherein z represents activation temperature Degree, a represents the quality of potassium hydroxide, and b represents the quality of compound, then the compound is M-P(1:1, and 700,2:1).100℃ Vacuum drying 10 h of degassing finally carry out CO2 saturation absorption to the compound of each temperature.Compound specific surface area after activation For 779.56 m2/g, 0.94 cm3/g of Kong Rongwei, average pore size is 6.42 nm, and the material is full to CO2 in 25 DEG C, 500 kPa It is 1.83 mmol/g with adsorbance.
From in embodiment 6-10 as can be seen that compound after being activated in embodiment 9, to the compound of each temperature into Row CO2 saturation absorption.Compound specific surface area after activation is 1119.14 m2/g, 0.60 cm3/g of Kong Rongwei, average pore size For 2.80 nm, which is 2.63 mmol/g to CO2 saturated extent of adsorption in 25 DEG C, 500 kPa.Adsorption effect is optimal, just Be say activated at 600 DEG C after adsorption effect it is best.
In the case that embodiment 9 is the potassium hydroxide and compound (KOH: compound=2, mass ratio) for weighing certain mass It is activated, in KOH: in the case that the mass ratio of compound is not 2, there can or can not be better adsorbance, with this end in view, It is tested.
Embodiment 10
The compound of M-P(1:1) is mixed with different proportion potassium hydroxide, is activated at 600 DEG C.Weigh certain matter The potassium hydroxide and compound (KOH: compound=4, mass ratio) of amount are stirred with glass bar up to uniform, in tubular type in porcelain boat It is once activated in furnace.Then compound obtains three kinds of products in 600 DEG C of 2 h of activation respectively in 200 DEG C of 1 h of activation, will Product ethyl alcohol and deionized water are alternately washed, until until neutrality, the compound abbreviation M-P(1:1, z, a:b), wherein z Represent activation temperature, a represents the quality of potassium hydroxide, and b represents the quality of compound, then the compound be M-P(1:1,600, 4:1).100 DEG C of vacuum drying 10 h of degassing, finally carry out CO2 saturation absorption to the compound of each ratio activation.After activation Compound specific surface area be 354.69 m2/g, 0.62 cm3/g of Kong Rongwei, average pore size be 1.42 nm, the material 25 DEG C, 500 kPa are 1.72 mmol/g to CO2 saturated extent of adsorption.
Embodiment 11
The compound of M-P(1:1) is mixed with different proportion potassium hydroxide, is activated at 600 DEG C.Weigh certain matter The potassium hydroxide and compound (KOH: compound=1, mass ratio) of amount are stirred with glass bar up to uniform, in tubular type in porcelain boat It is once activated in furnace.Then compound obtains three kinds of products in 600 DEG C of 2 h of activation respectively in 200 DEG C of 1 h of activation, will Product ethyl alcohol and deionized water are alternately washed, until until neutrality, the compound abbreviation M-P(1:1, z, a:b), wherein z Represent activation temperature, a represents the quality of potassium hydroxide, and b represents the quality of compound, then the compound be M-P(1:1,600, 1:1).100 DEG C of vacuum drying 10 h of degassing, finally carry out CO2 saturation absorption to the compound of each ratio activation.After activation Compound specific surface area be 739.81 m2/g, 0.063 cm3/g of Kong Rongwei, average pore size be 5.13 nm, the material 25 DEG C, 500 kPa are 2.39 mmol/g to CO2 saturated extent of adsorption.
Integrated embodiment 1-11, embodiment 9 are most preferred embodiment, and the compound specific surface area that embodiment 9 obtains is 0.60 cm3/g of 1119.14 m2/g, Kong Rongwei, average pore size are 2.80 nm, which is saturated CO2 in 25 DEG C, 500 kPa Adsorbance is 2.63 mmol/, and adsorbance is optimal
The present invention is compared with existing solid absorption technology, the solid absorbent of preparation not only specific surface area height, Kong Rong great, porosity Height, the rate of adsorption are fast, and thermal stability is high, adsorption desorption cycle performance is strong, regeneration energy consumption is low, are a kind of CO2 efficiently, environmentally friendly Adsorbent has a good application prospect and environmental improvement benefit.
Although the present invention has been described by way of example and in terms of the preferred embodiments, they be not it is for the purpose of limiting the invention, it is any ripe This those skilled in the art is practised, without departing from the spirit and scope of the invention, can make various changes or retouch from working as, therefore guarantor of the invention Shield range should be subject to what claims hereof protection scope was defined.

Claims (10)

1. a kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base, comprising the following steps: step 1: The processing of multi-walled carbon nanotube substrate carboxylation, specifically: multi-walled carbon nanotube and nitration mixture are flowed back at 80-100 DEG C and stir 80- 100 min, then cool to room temperature, and filter after being diluted with distilled water, alternately wash composite wood with dehydrated alcohol and deionized water Material is until neutral, then 55-65 DEG C of drying in a vacuum drying oven, grind into powder;Step 2: multi-walled carbon nanotube and aniline The quality of monomer is respectively 3-30:1, is dissolved in molten as mixing in the aqueous hydrochloric acid solution for 1 mol/L that volume is 150 mL Liquid goes to the mixed solution in three-necked flask under 0-5 DEG C, the temperature of 100-200 r/min and stirring condition, continues It is stirred to react 5-7 h, 25-35 min is then stirred by ultrasonic, step 3: weighing the 1mol/ that ammonium persulfate 3-3.5 g is dissolved in 50 mL U-shaped constant pressure titration funnel is poured into the aqueous hydrochloric acid solution of L, after ultrasonic vibration, is added drop-wise in three-necked flask in 30 min;Step 4: The reaction 5-7 h at 0-5 DEG C, the product ethyl alcohol that reaction is obtained, deionized water are alternately washed, centrifugation, in product is in Property, then freeze-drying process, grind into powder.
2. the method as described in claim 1, it is characterised in that: further include step 5, weigh the potassium hydroxide that mass ratio is 1:4 It is stirred with glass bar in porcelain boat until uniformly, once being activated in tube furnace, compound with compound made from step 4 In 200 DEG C of 1 h of activation, then in 300-700 DEG C of activation 1-3h, step 6: the compound after activation first being handled with acid, then It is alternately washed with ethyl alcohol, deionized water, centrifugation is finally placed in 50-70 DEG C of drying in vacuum oven until product is in neutrality, Grind into powder.
3. the method as described in claim 1, it is characterised in that: in step 4, the freeze-drying process is to use product Liquid-nitrogen freeze drying is subsequently placed under freeze drier is 18-22 Pa in -45 DEG C to -55 DEG C, vacuum degree and handles.
4. method as claimed in claim 3, it is characterised in that: logical nitrogen rate is 55-65 mL/min.
5. the method as described in claim 1, it is characterised in that: in step 4, centrifugal rotational speed is 6000-8000 r/min.
6. method according to claim 2, it is characterised in that: in step 6, centrifugal rotational speed is 6000-8000 r/min.
7. method according to claim 2, it is characterised in that: in step 6, acid is mass ratio 10% in the acid processing Hydrochloric acid.
8. such as method as claimed in any one of claims 1 to 7, it is characterised in that: the nitration mixture is the concentrated sulfuric acid, dense nitre 3:1 is mixed acid by volume.
9. such as method as claimed in any one of claims 1 to 7, it is characterised in that: the aqueous hydrochloric acid solution is by concentration The hydrochloric acid solution of 0.9-1.1 mol/L is diluted in deionized water for the concentrated hydrochloric acid of 36-38%.
10. such as method as claimed in any one of claims 1 to 7, it is characterised in that: the multi-walled carbon nanotube, caliber For 10-30 nm, length is 1-3 μm.
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